Atroposelective Three-Component (Fluoro)methylative Alkylation of Terminal Alkynes DOI

Yaheng Zhao,

Liping Huo,

Xiaoyu Zhao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 63 - 71

Published: Dec. 13, 2024

The development of synthetic methods for the selective installation methyl and fluoromethyl groups is highly desired due to their critical role in drug development. While significant advances have been made methylation difluoromethylation aromatic compounds, catalytic atroposelective (fluoro)methylative functionalization alkynes forge axially chiral alkenes remains underexploited. Herein, we report an enantioselective cross-electrophile strategy efficient 1,2-carbo-(fluoro)methylation with two different alkyl halides via nickel catalysis. By integrating a one-electron radical process two-electron organometallic process, this protocol employs simple catalyst effectively discriminate between secondary tertiary (fluoro)methyl alkyne difunctionalization. This demonstrates good compatibility activated secondary/tertiary bromides, terminal alkynes, halides, permitting straightforward synthesis broad range synthetically valuable (fluoro)methyl-substituted high chemo-, regio-, trans-, atropo-selectivity. Preliminary mechanistic studies provide insight into potential reaction pathway.

Language: Английский

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

Citations

42
Synthesis of Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols DOI
Ping Wu,

Wen‐Tao Zhang,

Jixiang Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Language: Английский

Citations

9
Asymmetric Sulfonylation from a Reaction of Cyclopropan-1-ol, Sulfur Dioxide, and 1-(Alkynyl)naphthalen-2-ol DOI
Chun Zhang, Shengqing Ye, Jie Wu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3321 - 3325

Published: April 10, 2024

Asymmetric sulfonylation from a reaction of cyclopropan-1-ol, sulfur dioxide, and 1-(alkynyl)naphthalen-2-ol in the presence catalytic amount organocatalyst at room temperature is developed. Axially chiral (S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols are generated moderate to good yields with excellent enantioselectivity regioselectivity under mild conditions. During this transformation, γ-keto sulfinate situ cyclopropan-1-ol dioxide acts as key intermediate.

Language: Английский

Citations

8
Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes DOI
Wangyang Li, Haohua Chen,

Yanping Zheng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11318 - 11331

Published: July 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Language: Английский

Citations

8
Organocatalytic Activation of Alkynes Enabled Remote Control of Atroposelectivity via Vinylidene para-Quinone Methides DOI
Yuan Cui, Yong‐Bin Wang, Huanhuan Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

Axially chiral o-VQMs have been extensively investigated as key intermediates to approach miscellaneous structures. By sharp contrast, their structural isomers p-VQMs not previously documented. The major reason, which results in the significant delay, may ascribe inherent challenges enantioselective activation of alkynes a remote manner. Herein, we demonstrate that mechanism para-hydroxyl-substituted arylacetylenes enables stereochemical induction, resulting axially aryl-alkenes with excellent enantiopurities. A series control experiments are performed elucidate insights this asymmetric transformation and verify involvement multimolecular CPAs reaction process. These findings expected unlock new feature for VQM chemistry inspire investigation into organocatalytic stereoselectivity.

Language: Английский

Citations

1
Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides DOI

Yi-Xin Wang,

Jing-Run Wang,

Chen Cui

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060

Published: Feb. 20, 2025

Language: Английский

Citations

1
Enantioselective organocatalytic synthesis of axially chiral aldehyde-containing styrenes via SNAr reaction-guided dynamic kinetic resolution DOI Creative Commons

Fengyuan Guo,

Siqiang Fang,

Jiajia He

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 19, 2023

The precise and efficient construction of axially chiral scaffolds, particularly toward the aryl-alkene atropoisomers with impeccably full enantiocontrol highly structural diversity, remains greatly challenging. Herein, we disclose an organocatalytic asymmetric nucleophilic aromatic substitution (SNAr) reaction aldehyde-substituted styrenes involving a dynamic kinetic resolution process via hemiacetal intermediate, offering novel facile way to significant axial styrene scaffolds. Upon treatment aldehyde-containing bearing (o-hydroxyl)aryl unit commonly available fluoroarenes in presence peptide-phosphonium salts, SNAr exquisite bridged biaryl lactol intermediate undergoes smoothly furnish series decorated various functionalities bioactive fragments high stereoselectivities (up >99% ee) complete E/Z selectivities. These resulting motifs are important building blocks for preparation diverse functionalized styrenes, which have great potential as privileged ligands/catalysts synthesis.

Language: Английский

Citations

18
Axially chiral styrene-based organocatalysts and their application in asymmetric cascade Michael/cyclization reaction DOI Creative Commons
Hao Yu,

Zi-Hao Li,

Zhi‐Gang Ma

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(35), P. 9496 - 9502

Published: Jan. 1, 2023

An axially chiral styrene-based organocatalyst, featuring a combination of structure and pyrrole ring, has been designed synthesized. This catalyst demonstrates remarkable capabilities in producing wide range densely substituted spirooxindoles that feature an alkyne-substituted quaternary stereogenic center. These are generated through mild cascade Michael/cyclization reactions, resulting high conversion rates exceptional enantioselectivity. Our catalytic model, based on experiments, X-ray analysis DFT calculations suggests matched π-π interactions multiple H-bonds between the organocatalyst substrates play significant roles controlling stereoselectivity reaction.

Language: Английский

Citations

14
Enantioselective Aminative Dearomatization of Indoles via Electrophilic 1,6-Addition of p-Quinone Diimides (p-QDIs) DOI

Parbat Subba,

Sushree Ranjan Sahoo,

Chhavi Khajuria

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4932 - 4937

Published: June 3, 2024

Herein we report the first use of p-quinone diimide for aminative dearomatization 2,3-disubstituted indoles to furnish C3 aza-quaternary chiral indolenines. This approach, which proceeds via an electrophilic 1,6-addition diimide, allows synthesis array optically active indolenines with high yields and excellent enantioselectivities. A one-pot approach same has also been established further improve synthetic accessibility this protocol.

Language: Английский

Citations

5
Ligand-Controlled Regiodivergent Ring Expansion of Benzosilacyclobutenes with Alkynes en Route to Axially Chiral Silacyclohexenyl Arenes DOI

Xiaoxiao Tang,

Yulang Tang,

Ju Peng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 21, 2024

A ligand-controlled regiodivergent and enantioselective ring expansion of benzosilacyclobutenes with internal naphthyl alkynes has been achieved by adjusting the ligand cavity size. The (

Language: Английский

Citations

5